Quaternary Ammonium Salt Detergents for Use in Fuels

ABSTRACT

A quaternary ammonium salt detergent made from the reaction product of the reaction of: (a) a hydrocarbyl substituted acylating agent and a compound having an oxygen or nitrogen atom capable of condensing with said acylating agent and further having a tertiary amino group; and (b) a quaternizing agent suitable for converting the tertiary amino group to a quaternary nitrogen and the use of such quaternary ammonium salt detergents in a fuel composition to reduce intake valve deposits.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority from application No. 60/691,115.

BACKGROUND OF THE INVENTION

The composition of the present invention related to a quaternaryammonium salt detergent and the use of such quaternary ammonium saltdetergents in a fuel composition to reduce intake valve deposits andremove or clean up existing deposits on the intake valves.

It is well known that liquid fuel contains components that can degradeduring engine operation and form deposits. These deposits can lead toincomplete combustion of the fuel resulting in higher emission andpoorer fuel economy. Fuel additives, such as detergents, are well knownadditives in liquid fuels to help with control or minimize depositformation. As the dynamics and mechanics of an engine continual advance,the requirements of the fuel must evolve to keep up with these engineadvancements. For example, today's engines have injector system thathave smaller tolerances and operate at higher pressure to enhance fuelspray to the compression or combustion chamber. Deposit prevention anddeposit reduction in these new engines has become critical to optimaloperation of today's engines. Advancements in fuel additive technology,such as detergents, have enabled the fuel to keep up with these engineadvancements. Therefore there is a need for detergent capable ofproviding acceptable performance in a liquid fuel to promote optimaloperation of today's engines.

U.S. Pat. No. 5,000,792 discloses polyesteramine detergent obtainable byreacting 2 parts of polyhydroxycarboxylic acids with 1 part ofdialkylenetriamine.

U.S. Pat. No. 4,171,959 discloses a motor fuel composition containingquaternary ammonium salts of a succinimide. The quaternary ammonium salthas a counterion of a halide, a sulphonate or a carboxylate.

U.S. Pat. No. 4,338,206 and U.S. Pat. No. 4,326,973 discloses fuelcompositions containing a quaternary ammonium salt of a succinimide,wherein the ammonium ion is heterocyclic aromatic (pyridinium ion).

U.S. Pat. No. 4,108,858 discloses a fuel or lubricating oil compositioncontaining a C2 to C4 polyolefin with a Mw of 800 to 1400 salted with apyridinium salt.

U.S. Pat. No. 5,254,138 discloses a fuel composition containing areaction product of a polyalkyl succinic anhydride with a polyaminohydroxyalkyl quaternary ammonium salt.

U.S. Pat. No. 4,056,531 discloses a lubricating oil or fuel containing aquaternary ammonium salt of a hydrocarbon with a Mw of 350 to 3000bonded to triethylenediamine. The quaternary ammonium salt counterion isselected from halides, phosphates, alkylphosphates, dialkylphosphates,borates, alkylborates, nitrites, nitrates, carbonates, bicarbonates,alkanoates, and O,O-dialkyldithiophosphates.

U.S. Pat. No. 4,248,719 discloses a fuel or lubricating oil containing aquaternary ammonium salt of a succinimide with a monocarboxylic acidester. U.S. Pat. No. 4,248,719 does not teach, suggest or otherwisedisclose low sulphur fuels, presence of fluidisers etc. Example 1teaches polyisobutylene succinimide with DMAPA as the amine. Thesuccinimide is then reacted with a salicylate.

U.S. Pat. No. 4,253,980 and U.S. Pat. No. 4,306,070 disclose a fuelcomposition containing a quaternary ammonium salt of an ester-lactone.

U.S. Pat. No. 3,778,371 discloses a lubricating oil or fuel containing aquaternary ammonium salt of a hydrocarbon with a Mw of 350 to 3000; andthe remaining groups to the quaternary nitrogen are selected from thegroup of C1 to C20 alkyl, C2 to C8 hydroxyalkyl, C2 to C20 alkenyl orcyclic groups.

The present invention, therefore, promotes optimal engine operation,that is, increased fuel economy, better vehicle drivability, reducedemissions and less engine maintenance by reducing, minimizing andcontrolling deposit formation.

SUMMARY OF THE INVENTION

The present invention further provides a method for fueling an internalcombustion engine, comprising:

A. supplying to said engine:

-   -   i. a fuel which is liquid at room temperature; and    -   ii. quaternary ammonium salt comprising the reaction product of:        -   (a) the reaction of a hydrocarbyl substituted acylating            agent and a compound having an oxygen or nitrogen atom            capable of condensing with said acylating agent and further            having a tertiary amino group; and        -   (b) a quaternizing agent suitable for converting the            tertiary amino group to a quaternary nitrogen    -   wherein the quaternizing agent is selected from the group        consisting of dialkyl sulfates, benzyl halides, hydrocarbyl        substituted carbonates; hydrocarbyl epoxides in combination with        an acid or mixtures thereof.

The present invention additionally provides for composition comprisingan quaternary ammonium salt which comprises the reaction product of:

a. the reaction of a hydrocarbyl-substituted acylating agent and acompound having an oxygen or nitrogen atom capable of condensing withsaid acylating agent and further having a tertiary amino group; and

b. a quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen

-   -   wherein the quaternizing agent is selected from the group        consisting of dialkyl sulfates, benzyl halides, hydrocarbyl        substituted carbonates; hydrocarbyl epoxides in combination with        an acid or mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

Various preferred features and embodiments will be described below byway of non-limiting illustration.

FIELD OF THE INVENTION

This invention involves a quaternary ammonium salt, a fuel compositionthat includes the quaternary ammonium salt, and a method of operating aninternal combustion engine with the fuel composition. The compositionsand methods of the present invention minimize, reduce and controldeposit formation in the engine, which reduces fuel consumption,promotes drivability, vehicle maintenance, and reduces emissions whichenables optimal engine operation.

Fuel

The composition of the present invention can comprise a fuel which isliquid at room temperature and is useful in fueling an engine. The fuelis normally a liquid at ambient conditions e.g., room temperature (20 to30° C.). The fuel can be a hydrocarbon fuel, a nonhydrocarbon fuel, or amixture thereof. The hydrocarbon fuel can be a petroleum distillate toinclude a gasoline as defined by ASTM specification D4814 or a dieselfuel as defined by ASTM specification D975. In an embodiment of theinvention the fuel is a gasoline, and in other embodiments the fuel is aleaded gasoline, or a nonleaded gasoline. In another embodiment of thisinvention the fuel is a diesel fuel. The hydrocarbon fuel can be ahydrocarbon prepared by a gas to liquid process to include for examplehydrocarbons prepared by a process such as the Fischer-Tropsch process.The nonhydrocarbon fuel can be an oxygen containing composition, oftenreferred to as an oxygenate, to include an alcohol, an ether, a ketone,an ester of a carboxylic acid, a nitroalkane, or a mixture thereof. Thenonhydrocarbon fuel can include for example methanol, ethanol, methylt-butyl ether, methyl ethyl ketone, transesterified oils and/or fatsfrom plants and animals such as rapeseed methyl ester and soybean methylester, and nitromethane. Mixtures of hydrocarbon and nonhydrocarbonfuels can include for example gasoline and methanol and/or ethanol,diesel fuel and ethanol, and diesel fuel and a transesterified plant oilsuch as rapeseed methyl ester. In an embodiment of the invention theliquid fuel is an emulsion of water in a hydrocarbon fuel, anonhydrocarbon fuel, or a mixture thereof. In several embodiments ofthis invention the fuel can have a sulphur content on a weight basisthat is 5000 ppm or less, 1000 ppm or less, 300 ppm or less, 200 ppm orless, 30 ppm or less, or 10 ppm or less. In another embodiment the fuelcan have a sulphur content on a weight basis of 1 to 100 ppm. In oneembodiment the fuel contains about 0 ppm to about 1000 ppm, about 0 toabout 500 ppm, about 0 to about 100 ppm, about 0 to about 50 ppm, about0 to about 25 ppm, about 0 to about 10 ppm, or about 0 to 5 ppm ofalkali metals, alkaline earth metals, transition metals or mixturesthereof. In another embodiment the fuel contains 1 to 10 ppm by weightof alkali metals, alkaline earth metals, transition metals or mixturesthereof. It is well known in the art that a fuel containing alkalimetals, alkaline earth metals, transition metals or mixtures thereofhave a greater tendency to form deposits and therefore foul or plugcommon rail injectors. The fuel of the invention is present in a fuelcomposition in a major amount that is generally greater than 50 percentby weight, and in other embodiments is present at greater than 90percent by weight, greater than 95 percent by weight, greater than 99.5percent by weight, or greater than 99.8 percent by weight.

Quaternary Ammonium Salt

The composition of the present invention comprises an quaternaryammonium salt which comprises the reaction product of (a.) the reactionof a hydrocarbyl-substituted acylating agent and a compound having anoxygen or nitrogen atom capable of condensing with said acylating agentand further having a tertiary amino group; and (b) a quaternizing agentsuitable for converting the tertiary amino group to a quaternarynitrogen wherein the quaternizing agent is selected from the groupconsisting of dialkyl sulfates, benzyl halides, hydrocarbyl substitutedcarbonates; hydrocarbyl epoxides in combination with an acid or mixturesthereof.

Examples of quaternary ammonium salt and methods for preparing the sameare described in the following patents, which are hereby incorporated byreference, U.S. Pat. No. 4,253,980, U.S. Pat. No. 3,778,371, U.S. Pat.No. 4,171,959, U.S. Pat. No. 4,326,973, U.S. Pat. No. 4,338,206, andU.S. Pat. No. 5,254,138.

The Hydrocarbyl Substituted Acylating Agent

The hydrocarbyl substituted acylating agent of the present invention isthe reaction product of a long chain hydrocarbon, generally a polyolefinsubstituted with a monounsaturated carboxylic acid reactant such as (i)α,β-monounsaturated C₄ to C₁₀ dicarboxylic acid such as fumaric acid,itaconic acid, maleic acid; (ii) derivatives of (i) such as anhydridesor C₁ to C₅ alcohol derived mono- or di-esters of (i);

(iii) α,β-monounsaturated C₃ to C₁₀ monocarboxylic acid such as acrylicacid and methacrylic acid; or (iv) derivatives of (iii) such as C₁ to C₅alcohol derived esters of (iii) with any compound containing an olefinicbond represented by the general formula:

(R¹)(R²)C═C(R⁶)(CH(R⁷)(R⁸))  (I)

wherein each of R¹ and R² is, independently, hydrogen or a hydrocarbonbased group. Each of R⁶, R⁷ and R⁸ is, independently, hydrogen or ahydrocarbon based group; preferably at least one is a hydrocarbon basedgroup containing at least 20 carbon atoms.

Olefin polymers for reaction with the monounsaturated carboxylic acidscan include polymers comprising a major molar amount of C₂ to C₂₀, e.g.C₂ to C₅ monoolefin. Such olefins include ethylene, propylene, butylene,isobutylene, pentene, octene-1, or styrene. The polymers can behomopolymers such as polyisobutylene, as well as copolymers of two ormore of such olefins such as copolymers of; ethylene and propylene;butylene and isobutylene; propylene and isobutylene. Other copolymersinclude those in which a minor molar amount of the copolymer monomerse.g., 1 to 10 mole % is a C₄ to C₁₈ diolefin, e.g., a copolymer ofisobutylene and butadiene; or a copolymer of ethylene, propylene and1,4-hexadiene.

In one embodiment, at least one R of formula (I) is derived frompolybutene, that is, polymers of C4 olefins, including 1-butene,2-butene and isobutylene. C4 polymers can include polyisobutylene. Inanother embodiment, at least one R of formula (I) is derived fromethylene-alpha olefin polymers, including ethylenepropylene-dienepolymers. Ethylene-alpha olefin copolymers and ethylene-lowerolefin-diene terpolymers are described in numerous patent documents,including European patent publication EP 0 279 863 and the followingU.S. Pat. Nos. 3,598,738; 4,026,809; 4,032,700; 4,137,185; 4,156,061;4,320,019; 4,357,250; 4,658,078; 4,668,834; 4,937,299; 5,324,800 each ofwhich are incorporated herein by reference for relevant disclosures ofthese ethylene based polymers.

In another embodiment, the olefinic bonds of formula (I) arepredominantly vinylidene groups, represented by the following formulas:

wherein R is a hydrocarbyl group

wherein R is a hydrocarbyl group.

In one embodiment, the vinylidene content of formula (I) can comprise atleast about 30 mole % vinylidene groups, at least about 50 mole %vinylidene groups, or at least about 70 mole % vinylidene groups. Suchmaterial and methods for preparing them are described in U.S. Pat. Nos.5,071,919; 5,137,978; 5,137,980; 5,286,823, 5,408,018, 6,562,913,6,683,138, 7,037,999 and U.S. Publication Nos. 20040176552A1,20050137363 and 20060079652A1, which are expressly incorporated hereinby reference, such products are commercially available by BASF, underthe tradename GLISSOPAL® and by Texas PetroChemical LP, under thetradename TPC 1105™ and TPC 595™.

Methods of making hydrocarbyl substituted acylating agents from thereaction of the monounsaturated carboxylic acid reactant and thecompound of formula (I) are well know in the art and disclosed in thefollowing U.S. Pat. Nos. 3,361,673 and 3,401,118 to cause a thermal“ene” reaction to take place; U.S. Pat. Nos. 3,087,436; 3,172,892;3,272,746, 3,215,707; 3,231,587; 3,912,764; 4,110,349; 4,234,435;6,077,909; 6,165,235 and are hereby incorporated by reference.

In another embodiment, the hydrocarbyl substituted acylating agent canbe made from the reaction of at least one carboxylic reactantrepresented by the following formulas:

wherein each of R³, R⁵ and R⁹ is independently H or a hydrocarbyl group,R⁴ is a divalent hydrocarbylene group and n is 0 or 1 with any compoundcontaining an olefin bond as represented by formula (I). Compounds andthe processes for making these compounds are disclosed in U.S. Pat. Nos.5,739,356; 5,777,142; 5,786,490; 5,856,524; 6,020,500; and 6,114,547.

In yet another embodiment, the hydrocarbyl substituted acylating agentcan be made from the reaction of any compound represented by formula (I)with (IV) or (V), and can be carried out in the presence of at least onealdehyde or ketone. Suitable aldehydes include formaldehyde,acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde,pentanal, hexanal. heptaldehyde, octanal, benzaldehyde, and higheraldehydes. Other aldehydes, such as dialdehydes, especially glyoxal, areuseful, although monoaldehydes are generally preferred. In oneembodiment, aldehyde is formaldehyde, which can be supplied as theaqueous solution often referred to as formalin, but is more often usedin the polymeric form as paraformaldehyde, which is a reactiveequivalent of, or a source of, formaldehyde. Other reactive equivalentsinclude hydrates or cyclic trimers. Suitable ketones include acetone,butanone, methyl ethyl ketone, and other ketones. Preferably, one of thetwo hydrocarbyl groups is methyl. Mixtures of two or more aldehydesand/or ketones are also useful.

Compounds and the processes for making these compounds are disclosed inU.S. Pat. Nos. 5,840,920; 6,147,036; and 6,207,839.

In another embodiment, the hydrocarbyl substituted acylating agent caninclude, methylene bis-phenol alkanoic acid compounds, the condensationproduct of (i) aromatic compound of the formula:

R_(m)—Ar-Z_(c)  (VI)

wherein R is independently a hydrocarbyl group, Ar is an aromatic groupcontaining from 5 to about 30 carbon atoms and from 0 to 3 optionalsubstituents such as amino, hydroxy- or alkyl-polyoxyalkyl, nitro,aminoalkyl, carboxy or combinations of two or more of said optionalsubstituents, Z is independently OH, lower alkoxy, (OR¹⁰)_(b)OR¹¹, or O—wherein each R¹⁰ is independently a divalent hydrocarbyl group, R¹¹ is Hor hydrocarbyl and b is a number ranging from 1 to about 30. c is anumber ranging from 1 to about 3 and m is 0 or an integer from 1 up toabout 6 with the proviso that m does not exceed the number of valencesof the corresponding Ar available for substitution and (ii) at least oncarboxylic reactant such as the compounds of formula (IV) and (V)described above. In one embodiment, at least one hydrocarbyl group onthe aromatic moiety is derived from polybutene. In one embodiment, thesource of hydrocarbyl groups are above described polybutenes obtained bypolymerization of isobutylene in the presence of a Lewis acid catalystsuch as aluminum trichloride or boron trifluoride.

Compounds and the processes for making these compounds are disclosed inU.S. Pat. Nos. 3,954,808; 5,336,278; 5,458,793; 5,620,949; 5,827,805;and 6,001,781.

In another embodiment, the reaction of (i) with (ii), optionally in thepresence of an acidic catalyst such as organic sulfonic acids,heteropolyacids, and mineral acids, can be carried out in the presenceof at least one aldehyde or ketone. The aldehyde or ketone reactantemployed in this embodiment is the same as those described above. Theratio of the hydroxyaromatic compound: carboxylic reactant:aldehyde orketone can be 2:(0.1 to 1.5):(1.9 to 0.5). In one embodiment, the ratiois 2:(0.8 to 1.1):(1.2 to 0.9). The amounts of the materials fed to thereaction mixture will normally approximate these ratios, althoughcorrections may need to be made to compensate for greater or lesserreactivity of one component or another, in order to arrive at a reactionproduct with the desired ratio of monomers. Such corrections will beapparent to the person skilled in the art. While the three reactants canbe condensed simultaneously to form the product, it is also possible toconduct the reaction sequentially, whereby the hydroxyaromatic isreacted first with either the carboxylic reactant and thereafter withthe aldehyde or ketone, or vice versa. Compounds and the processes formaking these compounds are disclosed in U.S. Pat. No. 5,620,949.

Other methods of making the hydrocarbyl substituted acylating agent canbe found in the following reference, U.S. Pat. Nos. 5,912,213;5,851,966; and 5,885,944 which are hereby incorporated by reference.

Compound Having a Nitrogen or Oxygen Atom

The composition of the present invention contains a compound having anoxygen or nitrogen atom capable of condensing with the acylating agentand further having a tertiary amino group.

In one embodiment, the compound having an oxygen or nitrogen atomcapable of condensing with the acylating agent and further having atertiary amino group can be represented by the following formulas:

wherein X is a alkylene group containing about 1 to about 4 carbonatoms; R2, R3 and R4 are hydrocarbyl groups.

wherein X is a alkylene group containing about 1 to about 4 carbonatoms; R3 and R4 are hydrocarbyl groups.

Examples of the nitrogen or oxygen contain compounds capable ofcondensing with the acylating agent and further having a tertiary aminogroup can include but are not limited to: dimethylaminopropylamine,N,N-dimethylaminopropylamine, N,N-diethyl-aminopropylamine,N,N-dimethylaminoethylamine ethylenediamine, 1,2-propylenediamine,1,3-propylene diamine, the isomeric butylenediamines, pentanediamines,hexanediamines, heptanediamines, diethylenetriamine,dipropylenetriamine, dibutylenetriamine, triethylenetetraamine,tetraethylenepentaamine, pentaethylenehexaamine, hexamethylenetetramine,and bis(hexamethylene)triamine, the diaminobenzenes, thediaminopyridines or mixtures thereof. The nitrogen or oxygen containingcompounds capable of condensing with the acylating agent and furtherhaving a tertiary amino group can further include aminoalkyl substitutedheterocyclic compounds such as 1-(3-aminopropyl)imidazole and4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine,3,3-diamino-N-methyldipropylamine,3′3-aminobis(N,N-dimethylpropylamine). Another type of nitrogen oroxygen containing compounds capable of condensing with the acylatingagent and having a tertiary amino group include alkanolamines includingbut not limited to triethanolamine, trimethanolamine,N,N-dimethylaminopropanol, N,N-diethylaminopropanol,N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine,N,N,N-tris(hydroxymethyl)amine.

Quaternizing Agent

The composition of the present invention contains a quaternizing agentsuitable for converting the tertiary amino group to a quaternarynitrogen wherein the quaternizing agent is selected from the groupconsisting of dialkyl sulfates, benzyl halides, hydrocarbyl substitutedcarbonates; hydrocarbyl epoxides in combination with an acid or mixturesthereof.

In one embodiment the quaternizing agent can include halides, such aschloride, iodide or bromide; hydroxides; sulphonates; alkyl sulphates,such as dimethyl sulphate; sultones; phosphates; C1-12 alkylphosphates;di C1-12 alkylphosphates; borates; C1-12 alkylborates; nitrites;nitrates; carbonates; bicarbonates; alkanoates; O,O-di C1-12alkyldithiophosphates; or mixtures thereof.

In one embodiment the quaternizing agent may be derived from dialkylsulphates such as dimethyl sulphate, N-oxides, sultones such as propaneand butane sultone; alkyl, acyl or aralkyl halides such as methyl andethyl chloride, bromide or iodide or benzyl chloride, and a hydrocarbyl(or alkyl) substituted carbonates. If the acyl halide is benzylchloride, the aromatic ring is optionally further substituted with alkylor alkenyl groups.

The hydrocarbyl (or alkyl) groups of the hydrocarbyl substitutedcarbonates may contain 1 to 50, 1 to 20, 1 to 10 or 1 to 5 carbon atomsper group. In one embodiment the hydrocarbyl substituted carbonatescontain two hydrocarbyl groups that may be the same or different.Examples of suitable hydrocarbyl substituted carbonates include dimethylor diethyl carbonate.

In another embodiment the quaternizing agent can be a hydrocarbylepoxides, as represented by the following formula, in combination withan acid:

wherein R1, R2, R3 and R4 can be independently H or a C1-50 hydrocarbylgroup.

Examples of hydrocarbyl epoxides can include, styrene oxide, ethyleneoxide, propylene oxide, butylene oxide, stilbene oxide and C2-50epoxide.

Oil of Lubricating Viscosity

The composition of the present invention can contain an oil oflubricating viscosity. The oil of lubricating viscosity includes naturalor synthetic oils of lubricating viscosity, oil derived fromhydrocracking, hydrogenation, hydrofinishing, unrefined, refined andre-refined oils, or mixtures thereof. In one embodiment the oil oflubricating viscosity is a carrier fluid for the dispersant and/or otherperformance additives.

Natural oils include animal oils, vegetable oils, mineral oils ormixtures thereof. Synthetic oils include a hydrocarbon oil, asilicon-based oil, a liquid ester of phosphorus-containing acid.Synthetic oils may be produced by Fischer-Tropsch reactions andtypically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes.

Oils of lubricating viscosity may also be defined as specified in theAmerican Petroleum Institute (API) Base Oil InterchangeabilityGuidelines. In one embodiment the oil of lubricating viscosity comprisesan API Group I, II, III, IV, V or mixtures thereof, and in anotherembodiment API Group I, II, III or mixtures thereof.

Miscellaneous

The composition optionally comprises one or more additional performanceadditives. The other performance additives include metal deactivators,detergents, dispersants, viscosity modifiers, friction modifiers,dispersant viscosity modifiers, extreme pressure agents, antiwearagents, antioxidants, corrosion inhibitors, foam inhibitors,demulsifiers, pour point depressants, seal swelling agents, wax controlpolymers, scale inhibitors, gas-hydrate inhibitors and mixtures thereof.

The total combined amount of the additional performance additivecompounds present on an oil free basis ranges from 0 wt % to 25 wt % or0.01 wt % to 20 wt % of the composition. Although one or more of theother performance additives may be present, it is common for the otherperformance additives to be present in different amounts relative toeach other.

In one embodiment the composition can be in a concentrate formingamount. If the present invention may be in the form of a concentrate(which may be combined with additional oil to form, in whole or in part,a finished lubricant and/or liquid fuel), the ratio of the additive ofthe invention and/or other additional performance additives in an oil oflubricating viscosity and/or liquid fuel, to diluent oil is in the rangeof 80:20 to 10:90 by weight.

Antioxidants include molybdenum dithiocarbamates, sulphurised olefins,hindered phenols, diphenylamines; detergents include neutral oroverbased, Newtonian or non-Newtonian, basic salts of alkali, alkalineearth and transition metals with one or more of phenates, sulphurisedphenates, sulphonates, carboxylic acids, phosphorus acids, mono- and/ordithiophosphoric acids, saligenins, an alkylsalicylates, salixarates.Dispersants include N-substituted long chain alkenyl succinimide as wellas posted treated version thereof, post-treated dispersants includethose by reaction with urea, thiourea, dimercaptothiadiazoles, carbondisulphide, aldehydes, ketones, carboxylic acids,hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boroncompounds, and phosphorus compounds.

Antiwear agents include compounds such as metal thiophosphates,especially zinc dialkyldithiophosphates; phosphoric acid esters or saltthereof; phosphites; and phosphorus-containing carboxylic esters,ethers, and amides. Antiscuffing agents including organic sulphides andpolysulphides, such as benzyldisulphide, bis-(chlorobenzyl) disulphide,dibutyl tetrasulphide, ditertiary butyl polysulphide,di-tert-butylsulphide, sulphurised Diels-Alder adducts or alkylsulphenyl N′N-dialkyl dithiocarbamates. Extreme Pressure (EP) agentsincluding chlorinated wax, organic sulphides and polysulphides, such asbenzyldisulphide, bis-(chlorobenzyl) disulphide, dibutyl tetrasulphide,sulphurised methyl ester of oleic acid, sulphurised alkylphenol,sulphurised dipentene, sulphurised terpene, and sulphurised Diels-Alderadducts; phosphosulphurised hydrocarbons, metal thiocarbamates, such aszinc dioctyldithiocarbamate and barium heptylphenol diacid.

Friction modifiers include fatty amines, esters such as borated glycerolesters, partial esters of glycerol such as glycerol monooleate, fattyphosphites, fatty acid amides, fatty epoxides, borated fatty epoxides,alkoxylated fatty amines, borated alkoxylated fatty amines, metal saltsof fatty acids, fatty imidazolines, condensation products of carboxylicacids and polyalkylenepolyamines, amine salts of alkylphosphoric acids.Viscosity modifiers include hydrogenated copolymers ofstyrene-butadiene, ethylene-propylene polymers, polyisobutenes,hydrogenated styrene-isoprene polymers, hydrogenated isoprene polymers,polymethacrylate acid esters, polyacrylate acid esters, polyalkylstyrenes, alkenyl aryl conjugated diene copolymers, polyolefins,polyalkylmethacrylates and esters of maleic anhydride-styrenecopolymers. Dispersant viscosity modifiers (often referred to as DVM)include functionalised polyolefins, for example, ethylene-propylenecopolymers that have been functionalized with the reaction product ofmaleic anhydride and an amine, a polymethacrylate functionalised with anamine, or styrene-maleic anhydride copolymers reacted with an amine.

Corrosion inhibitors include octylamine octanoate, condensation productsof dodecenyl succinic acid or anhydride and a fatty acid such as oleicacid with a polyamine. Metal deactivators include derivatives ofbenzotriazoles, 1,2,4-triazoles, benzimidazoles,2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles. Foaminhibitors include copolymers of ethyl acrylate and 2-ethylhexylacrylateand optionally vinyl acetate. Demulsifiers include polyethylene glycols,polyethylene oxides, polypropylene oxides and (ethylene oxide-propyleneoxide) polymers; pour point depressants including esters of maleicanhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.Seal swell agents include Exxon Necton-37™ (EN 1380) and Exxon MineralSeal Oil

INDUSTRIAL APPLICATION

In one embodiment the invention is useful as a liquid fuel for aninternal combustion engine. The internal combustion engine includesspark ignition and compression ignition engines; 2-stroke or 4-strokecycles; liquid fuel supplied via direct injection, indirect injection,port injection and carburetor; common rail and unit injector systems;light (e.g. passenger car) and heavy duty (e.g. commercial truck)engines; and engines fuelled with hydrocarbon and non-hydrocarbon fuelsand mixtures thereof. The engines may be part of integrated emissionssystems incorporating such elements as; EGR systems; aftertreatmentincluding three-way catalyst, oxidation catalyst, NOx absorbers andcatalysts, catalyzed and non-catalyzed particulate traps optionallyemploying fuel-borne catalyst; variable valve timing; and injectiontiming and rate shaping.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbylgroup” is used in its ordinary sense, which is well-known to thoseskilled in the art. Specifically, it refers to a group having a carbonatom directly attached to the remainder of the molecule and havingpredominantly hydrocarbon character. Examples of hydrocarbyl groupsinclude: hydrocarbon substituents, that is, aliphatic (e.g., alkyl oralkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, andaromatic-, aliphatic-, and alicyclic-substituted aromatic substituents,as well as cyclic substituents wherein the ring is completed throughanother portion of the molecule (e.g., two substituents together form aring); substituted hydrocarbon substituents, that is, substituentscontaining non-hydrocarbon groups which, in the context of thisinvention, do not alter the predominantly hydrocarbon nature of thesubstituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy,mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); heterosubstituents, that is, substituents which, while having a predominantlyhydrocarbon character, in the context of this invention, contain otherthan carbon in a ring or chain otherwise composed of carbon atoms.Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituentsas pyridyl, furyl, thienyl and imidazolyl. In general, no more than two,preferably no more than one, non-hydrocarbon substituent will be presentfor every ten carbon atoms in the hydrocarbyl group; typically, therewill be no non-hydrocarbon substituents in the hydrocarbyl group.

It is known that some of the materials described above may interact inthe final formulation, so that the components of the final formulationmay be different from those that are initially added. For instance,metal ions (of, e.g., a detergent) can migrate to other acidic oranionic sites of other molecules. The products formed thereby, includingthe products formed upon employing the composition of the presentinvention in its intended use, may not be susceptible of easydescription. Nevertheless, all such modifications and reaction productsare included within the scope of the present invention; the presentinvention encompasses the composition prepared by admixing thecomponents described above.

EXAMPLES

The invention will be further illustrated by the following examples,which sets forth particularly advantageous embodiments. While theexamples are provided to illustrate the present invention, they are notintended to limit it.

The detergents are evaluated in the engine nozzle fouling test, asdescribed in CEC F-23-01. The results of the engine nozzle fouling testare highlighted in Tables 1 and 2.

The detergents that are used in this test include: a commercialavailable 1000Mn polyisobutylene succinimide of dimethylaminopropylamine(Comparative Example 1), a commercially available 1000 Mnpolyisobutylene succinimide of tetraethylenepentamine (ComparativeExample 2) and 4 experimental detergents of the present invention(Examples 1-4) as described below.

Preparatory Example A

Preparatory Example A is prepared from a mixture of succinic anhydrideprepared from 1000 Mn polyisobutylene (21425 grams) and diluentoil-pilot 900 (3781 grams) which are heated with stirring to 110° C.under a nitrogen atmosphere. Dimethylaminopropylamine (DMAPA, 2314grams) is added slowly over 45 minutes maintaining batch temperaturebelow 115° C. The reaction temperature is increased to 150° C. and heldfor a further 3 hours. The resulting compound is a DMAPA succinimide.

Example 1

Reaction product of Preparatory Example A, styrene oxide (12.5 grams),acetic acid (6.25 grams) and methanol (43.4 grams) are heated withstirring to reflux (˜80° C.) for 5 hours under a nitrogen atmosphere.The reaction is purified by distillation (30° C., −1 bar) and gave awater white distillate. The resulting compound is a styrene oxidequaternary ammonium salt.

Example 2

Reaction product of Preparatory Example A (373.4 grams) is heated withstirring to 90° C. Dimethylsulphate (25.35 g) is charged to the reactionpot and stirring resumed (˜300 rpm) under a nitrogen blanket, exothermraises batch temperature to ˜100° C. The reaction is maintained at 100°C. for 3 hours before cooling back and decanting. The resulting compoundis a dimethylsulphate quaternary ammonium salt.

Example 3

Reaction product of Preparatory Example A (1735.2 grams) is heated withstirring to 90° C. under a nitrogen atmosphere. Benzyl chloride (115.4grams) is added drop wise maintaining reaction temperature at 90° C. Thereaction is held for 5 hours at 90° C. The resulting compound is abenzyl chloride quaternary ammonium salt.

Example 4

The reaction product of Preparatory Example A (152.6 grams), dimethylcarbonate (31 grams) and methanol (26.9 grams) is charged to a pressurevessel. The vessel is then pressure tested for leaks and purged withnitrogen twice. The vessel is pressurized to ˜19 psi and the batchheated to 90° C. with agitation (˜210 rpm). The batch is held ontemperature for one hour before being heated to 140° C. and held ontemperature for 24 hours. On cooling back to ambient temperatureresidual pressure is released before decanting product. The reaction waspurified by distillation (100° C., −0.5 bar) to remove free dimethylcarbonate and methanol. The resulting compound is a dimethyl carbonatequaternary ammonium salt.

Note: For Comparative Examples 1 and 2 the active chemical isaccompanied by inert diluent oil in a ratio of active chemical todiluent oil of 85:15 by weight.

Note: For Examples 1-4 the active chemical is accompanied by inertdiluent oil in a ratio of active chemical to diluent oil of 50:50 byweight.

TABLE 1 Results in the CEC F-23-01 Injector Deposit Test PercentRemaining Flow Detergent Dose Rate Active (ppm) (%) None* 0.0 11.0Example 1 17.5 73.2 Example 1 17.5 46.4 Example 2 17.5 31.0 Example 217.5 24 Example 3 17.5 33.7 Example 4 15 27.1 Note: *unadditized basefuel (no detergent present in the fuel)

TABLE 2 Results in the CEC F-23-01 Injector Deposit Test PercentRemaining Flow Detergent Dose Rate Active (ppm) (%) Comparative Ex. 2 5179 Comparative Ex. 2 51 63 Example 2 50 100 Example 2 50 98 ComparativeEx. 2 38.25 34 Comparative Ex. 2 38.25 32.4 Comparative Ex. 2 38.25 30Example 2 38.5 76 Example 4 38.5 41 Example 4 38.5 72 Example 4 38.5 84Comparative Ex. 1 38.25 84.0 Example 1 35.0 99.6 Example 1 35.0 84.8

The results of the test show that formulations using quaternary ammoniumsalt detergents of the present invention (Examples 1, 2, 3, and 4) showsequivalent or superior flow performance and less average blockage of aninjector compared to formulations using an unadditized fuel and/orcommercially available detergents (Comparative Examples 1 and 2).

The detergents are further evaluated in a High Speed Direct InjectionTest. The High Speed Direct Injection Test is described as follows. Adiesel fuel containing 1 ppm of zinc plus the respective detergent isinserted into a 2.0 L High Speed Direct Injection (HSDI) Ford Pumaengine. The engine is initially run at 2000 rev/minute for 5 minutes(engine warm-up period). After the initial warm up period, the engine isrun in six (6) power curve iterations under the conditions set forth inTable 3. After completion of the sixth power curve iteration, the engineis subjected to the stabilization period under the conditions set forthin Table 4. After the stabilization period is complete, the engine isrun in another six (6) power curve iterations under the conditions setforth in Table 3. The power output of the engine is measured during the9th stage of the power curve iteration. The power at this 9th stageduring the final power curve iteration (12th power curve iteration) iscompared to the power at the 9th stage of the first power curveiteration and a final power loss in percent is calculated. The lesspower loss present in the engine the more effective the detergent is atreducing or minimizing power loss. The results of the test aresummarized in Table 5.

The detergents that are used in this test include: a commercialavailable 1000Mn polyisobutylene succinimide of dimethylaminopropylamine(Comparative Example 1), a commercially available 1000 Mnpolyisobutylene succinimide of tetraethylenepentamine (ComparativeExample 2) and 3 experimental detergents of the present invention(Examples 1, 2 and 4) as described above.

TABLE 3 Power Curve Iteration Time Speed Stage (min) (rev/min) 1 5 1000± 10 2 5 1250 ± 10 3 5 1500 ± 10 4 5 1750 ± 10 5 5 2000 ± 10 6 5 2250 ±10 7 5 2500 ± 10 8 5 3000 ± 10 9 5 3300 ± 10 10 5 3500 ± 10 11 5 4000 ±10 NOTE: The ramping time between stages is 27 seconds except for theramp from Stage 11 back to Stage 1 which is 30 seconds. These ramp timesare not included in the stage times (i.e. total duration of the scheduleis (11*5 minute stages) + (10*27 second ramps) + (1* 30 second ramp)giving a total cycle time of 60 minutes).

TABLE 4 Stabilization Run Time Speed Load Stage (hrs) (rev/min) (N-m) 12 3000 ± 10 150 2 2 2020 ± 10 95 3 1 3500 ± 10 80

TABLE 5 Results in a High Speed Direct Injection Test Detergent DoseRate Active (ppm) % Power Loss at 17 hrs None 0.0 9.13 None 0.0 9.71Example 1 17.5 1.85 Example 2 17.5 3.15 Example 4 15 9.95 Comparative Ex1 38.25 8.35 Comparative Ex 1 38.25 6.48 Comparative Ex 2 38.25 5.30Note: * unadditized diesel base fuel (no detergent present in the fuel)

The results of the test show that formulations using quaternary ammoniumsalt detergents of the present invention (Examples 1, 2, and 4) produceequivalent or reduced power loss compared to formulations using aunadditized fuel and/or commercial available detergents (ComparativeExamples 1 and 2).

Each of the documents referred to above is incorporated herein byreference. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about.” Unless otherwise indicated, each chemical or compositionreferred to herein should be interpreted as being a commercial gradematerial which may contain the isomers, by-products, derivatives, andother such materials which are normally understood to be present in thecommercial grade. However, the amount of each chemical component ispresented exclusive of any solvent or diluent oil, which may becustomarily present in the commercial material, unless otherwiseindicated. It is to be understood that the upper and lower amount,range, and ratio limits set forth herein may be independently combined.Similarly, the ranges and amounts for each element of the invention canbe used together with ranges or amounts for any of the other elements.As used herein, the expression “consisting essentially of” permits theinclusion of substances that do not materially affect the basic andnovel characteristics of the composition under consideration.

1. A composition comprising a quaternary ammonium salt which comprisesthe reaction product of: a. the reaction of a hydrocarbyl-substitutedacylating agent and a compound having an oxygen or nitrogen atom capableof condensing with said acylating agent and further having a tertiaryamino group; and b. quaternizing agent suitable for converting thetertiary amino group to a quaternary nitrogen wherein the quaternizingagent is selected from the group consisting of dialkyl sulfates, benzylhalides, hydrocarbyl substituted carbonates; hydrocarbyl epoxides incombination with an acid or mixtures thereof.
 2. The composition ofclaim 1, wherein the hydrocarbyl-substituted acylating agent ispolyisobutylene succinic anhydride.
 3. The composition of claim 1,wherein the compound of (a) is a N-methyl-1,3-diaminopropane.
 4. Thecomposition of claim 1, further comprising a fuel which is liquid atroom temperature.
 5. The method of fueling an internal combustion enginecomprising: A. supplying to said engine: i. a fuel which is liquid atroom temperature; and ii. quaternary ammonium salt comprising thereaction product of: (a) the reaction of a hydrocarbyl substitutedacylating agent and a compound having an oxygen or nitrogen atom capableof condensing with said acylating agent and further having a tertiaryamino group; and (b) a quaternizing agent suitable for converting thetertiary amino group to a quaternary nitrogen wherein the quaternizingagent is selected from the group consisting of dialkyl sulfates, benzylhalides, hydrocarbyl substituted carbonates; hydrocarbyl epoxides incombination with an acid or mixtures thereof.
 6. The composition ofclaim 1, further comprising an oil of lubricating viscosity.
 7. Thecomposition of claim 6, further comprising component selected from thegroup consisting of metal deactivators, detergents other than those ofclaim 1, dispersants, viscosity modifiers, friction modifiers,dispersant viscosity modifiers, extreme pressure agents, antiwearagents, antioxidants, corrosion inhibitors, foam inhibitors,demulsifiers, pour point depressants, seal swelling agents, wax controlpolymers, scale inhibitors, gas-hydrate inhibitors and mixtures thereof.8. The composition of claim 7, wherein the component is an overbasedmetal containing detergent, zinc dialkyldithiophosphates or mixturesthereof.